Organotin or mercury (carboxy hydrocarbylene amides)



United States Patent US. Cl. 260-429.7 15 Claims ABSTRACT OF THE DISCLOSURE organometallic salts of the formula RI! m I wherein R is an organic radical, R and R" are selected from the group consisting of aliphatic radicals of 1 to 18 carbon atoms, cycloaliphatic radicals of 3 to 8 carbon atoms, aryl radicals and araliphatic radicals, R' is selected from the group consisting of hydrogen, aliphatic radicals of 1 to 18 carbon atoms, cycloaliphatic radicals of 3 to 8 carbon atoms, aryl radicals and araliphatic radicals and R and R' taken together with the nitrogen atom may form a heterocyclic radical, M is a metal in its highest state of oxidation and n and m are integers from 1 to 3, and m+n is not greater than 4.

The organometallic salts of Formula I have a wide range of biocidal activity and are useful as bactericides, fungicides, nematocides, acaricides, insecticides and as preand post-emergence herbicides.

OBJECTS OF THE INVENTION It is an object of the invention to matellic salts of Formula I.

It is another object of the invention to provide novel biocidally active compositions.

These and other objects and advantages of the invention will become obvious from the following detailed description.

provide novel organo- THE INVENTION The novel organometallic salts of the invention have the RI! m I highest state of oxidation and n and m are integers from 1 to 3, and m:+n is not greater than 4.

The salts of Formula I are derived from monoamides of dicarboxylic acids which may be aliphatic, aromatic, cycloaliphatic or heterocyclic. Examples of suitable dicarboxylic acids whose monoamides are used to form the organometallic salts of the invention are aliphatic dicarboxylic acids such as maleic acid, :fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, citraconic acid, itaconic acid, etc.; aromatic acids such as phthalic acid, terephthalic acid, isophthalic acid, hydroxyphthalic acid, xylidic acid, uvitic acid, cumidic acid, 1,5-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, etc.; cyclo aliphatic dicarboxylic acids such as dihydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrahydroterephthalic acid, tetrahydroisophthalic acid, hexahydroisophthalic acid, etc.; and heterocyclic dicarboxylic acids such as quinolinic acid, lutidinic acid, isocinchomeronic acid, dipiolinic acid, dinicotinic acid, etc.

The amide portion of the amic acids is derived from aliphatic, cycloaliphatic, aromatic, araliphatic and heterocyclic amines. Examples of suitable amines are aliphatic amines such as methyl amine, dimethylamine, butyl amine, hexyl amine, oleylamine, dipropylamine, etc.; aromatic amines such as aniline, p-bromo aniline, 3- methoxy aniline, naphthylamine, 3,4-dichloroaniline, 4- methylaniline, etc.; araliphatic amines such as benzylamine, phenethylamine, etc.; cycloaliphatic amines such as cyclohexylamine, etc.; and heterocyclic amines such as morpholine, piperidine, piperazine, pyrrolidine, etc.

The organometallic salts of Formula I can be prepared by reacting the appropriate amic acid with the desired organometallic oxide and hydroxide in an inert organic solvent or by reacting a salt of the desired amic acid with an appropriate organometallic salt.

Examples of suitable metals which are employed in their highest state of oxidation or highest valence state are mercury, tin, lead, germanium, silicon, etc.

Preferred organometallic compounds of Formula I are compounds wherein R and R" are selected from the group consisting of alkyl of 1 to 10 carbon atoms, halogenated alkyl of 1 to '10 carbon atoms, alkenyl and alkynyl radicals of 1 to 10 carbon atoms, cycloalkyl radicals of 4 to 8 carbon atoms, naphthyl, phenyl and phenyl substituted with at least one substituent selected from the group consisting of halogen, lower alkyl and halogenated lower alkyl of 1 to 7 carbon atoms, hydroxy, lower alkoxy of 1 to 7 carbon atoms and nitro and R" may be selected from the same group as R' or hydrogen.

The said compounds can be formulated into various forms such as concentrates, emulsions, solutions, pastes, wettable powders, etc. depending upon the desired use. In order to prepare a solution suitable for direct spraying there may be used, for example, a mineral oil fraction of high or medium boiling range, such as diesel oil or kerosene, or coal tar oils, or vegetable or animal oils and also hydrocarbons such as alkylated naphthalenes, or tetrahydronaphthalene, if desired, with the use of xylene mixtures, cyclohexanols, ketones, or chlorinated hydrocarbons, such as tetrachloroethane, trichloroethylene or trior tetrachlorobenzenes.

Aqueous preparations suitable for application can be prepared by the addition of water to emulsion concentrates, pastes or wettable powders. As emulsifying or dispersing agents there may be used non-ionic products, for example, condensation products of ethyleneoxide with aliphatic alcohols, amines or carboxylic acids containing a hydrocarbon radical having about to 30 carbon atoms, such as a condensation product of octadccyl alcohol with to molecular proportions of ethylene oxide, or of soya bean fatty acid with 30 molecular proportions of ethylene oxide or of commercial oleylamine ;with 15 molecular proportions of ethylene oxide or of dodecylmercaptan with 12 molecular proportions of ethyleneoxide. Among anion active emulsifying agents there may be mentioned the sodium salt of dodecyl alcohol sulfuric acid ester, the sodium salt of dodecyl-benzsene sulfonic acid, the potassium or tricthanolamine salt of oleic acid or abietic acid or of a mixture of these acids, or the sodium salt of petroleum-sulfonic acid. As cation-active dispersing agents there may be used, quaternary ammonium compounds, such as cetyl-pyridinium bromide or di(hydroxyet hyl)-benzyl-do decyl-ammonium chloride.

For making dusting or scattering preparations there may be used as solid carriers talcum kaolin, bentonite, calcium carbonate or calcium phosphate or carbon, cork meal or wood meal or other materials of vegetable origin. The various preparations can be rendered more suitable for the various ways in which they are to be used by the known addition of substances which improve the dispersion, adhesiveness, resistance to rain or penetration capacity of the compositions. As such substances there may be mentioned fatty acids, resins, glue, casein or, for example, alginates or the like.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

Example I.-Preparation of triphenyltin 3',4'- dichlorosuccinanilate Example II Using the procedure of Example I, triethiyltin hydroxide was reacted with N-hexylmaleamic acid to form triethyltin N-hexylmaleamate having a melting point of 79 to 81.5 C. and containing 29.86% tin and 3.42% nitrogen (theoretical-29.38% tin and 3.47% N).

Example III Using the procedure of Example I, tributyltin hydroxide was reacted with N-hexylm'aleamic acid to form tributyltin N-hexylrnaleamate as an oil containing 23.95% tin (theoretical24.34%

Example IV I, triphenyltin hydroxacid to form trimelting point of tin (theoretical- Using the procedure of Example ide was reacted with N-hexylrnaleamic phcnyltin N-hexylmaleamate having a 126 to 127.5 C. and containing 21.77% 21.66%

Example V Using the procedure of Example I, triethyltin hydroxide and 3,4'-dichloromaleanilic acid were reacted to form triethyltin 3',4'-dichloromaleanilate having a melting point of 139 to 141 C. and containing 25.98% tin and 3.09% N (theoretical25.53% tin and 3.01% N).

Example VI Using the procedure of Example I, tributyltin hydroxide was reacted with 3',4-dichloromaleanilic acid to form tributyltin 3',4dichloromaleanilate having a melting point of 89.5 to C. and containing 21.76% tin (theoretical21.62%

Example VII Using the procedure of Example I, triphenyltin hydroxide was reacted with 3',4'-dichloromaleanilic acid to form triphenyltin 3,4'-dichloromaleanilate having a melting point of to 156.5 C. and containing 1 9.61% tin (theoretical19.49%

Example VIII Using the procedure of Example I, tributyltin hydroxide was reacted with 3',4-dichlorosuccinanilic acid to form tributyltin 3,4-dichlorosuccinanilate having a melting point of 15 8-i159 C.

Example IX Using the procedure of Example I, tributyltin hydroxide was reacted with 3'-chlorosuccinanilic acid to form tributyltin 3-chlorosuccinnanilate having a melting point of 60 to 64 C.

Example X Using the procedure of Example I, tributyltin hydroxide was reacted with 3-trifiuoromethylsuccinanilic acid to form tributyltin 3'-trifiuoromethylsuccinanilate having a melting point of 69' to 72 C.

Example XI Using the procedure of Example I, tributyltin hydroxide was reacted with 4'-chloro-3'-trifiuoromethylsuccinanilic acid to form tributyltin 4-chloro-3-trifiuoromethylsuccinanilate having a melting point of 63 to 66 C.

Example XII Using the procedure of Example I, tributyltin hydroxide was reacted with N,N-diethylsuccinamic acid to form tributyltin N,N-diethylsuccinamate having a melting point of 70 to 72 C.

Example XIII Using the procedure of Example I, tributyltin hydroxide was reacted with N,N-di-n-propylsuccinamic acid to form tributyltin N,N-di-n-propylsuccinamate having a melting point of 56 to 59 C.

Example XIV 0.1 mol of sodium N-hexylmaleamate and 0.1 mol of phenylmercuric chloride were added to a flask containing 500 cc. of benzene and the mixture was refluxed with stirring for 3 days after which the benzene was removed by distillation. The residue was washed with water and dried to obtain a white powder of phenylmercuric N hexylmaleamate which did not melt below 300 C. and contained 2.90% N (theoretical2.94%).

BIOCIDAL ACTIVITY A. Nematocidal activity The tests were carried out in stoppered test tubes containing 10 cc. of the solution to be tested and the nematode population at the time of seeding was adjusted to 50 to 75 per tube. The tests were run in duplicate and the blanks contained the nema in tap water. The organism used was a species of Panagrellus, an active saprozoic nematode. Daily microscopic observations of the nema were made to determine the percent of mortality which was easily determined because of the constant and active movement of live nema of this species. The test results are summarized in Table I.

TABLE I Percent mortality after days Dosage, Compound p.p.m. 1 2 4 5 6 7 Phenylmercuric N-hexylmaleamate Triethyltin N-hexylmaleamate Tributyltin N-hexylmaleamate Triphenyltin N-hexylmaleamate Triethyltin 3,4-dichloromaleanilate Tributyltin 3,4-dichloromaleanilate Tributyltin-4-chloro3-CF -sucoinanilate Tributyltin-N,N-diethy1 succinamate Tributyltin N,N-dipropyl succinamato Nemagon Control Table I shows that the organometallic compounds have TABLE III a greater nematocidal activity than the commercial nema- Percent toclde, Nemagon, which is l,2-d1brom0-3-chloropropane. Dosage, Disease Gamma mlcal p.p.m. Control tion B. Seed disinfectant actlvity 500 100 0 Oat seeds heavily infected With Helmzznthosporiz m Phenylmemuric N 23 avenue was lmmersed for 15 minutes 1n solutions contarn- 62 100 36 ing various concentrations of the test compounds after 58 3g 5% which the solutions were drained olf and the seeds were 250 90 79 fi Panogen-15 125 96 69 then plated out on Petri dishes contalnmg moistened lter 62 70 80 paper. The results are summarized in Table II. C 31.5 12 so heck 74 Table III shows that phenylmercuric N-hexylmaleamate TABLE II 40 1s a far superior seed drslnfectant than Panogen-IS. S1nce Percent the said test was conducted on a weight basis rather than Dosage, Disease Germination on a molar basis, it is important to consider that phenyl- Compound p-p- Control Oat Seeds mercuric N-hexylmaleamaate has a molecular weight 1.6 Phenylmercuric N hexylmalea- 5,000 100 0 times that of Panogen-lS and on a molar basis the results mate 88 8 are even more striking.

5,000 100 0 Triethyltin N hexylmaleamate egg igg M0 C. Insecticidal activity 5, 000 100 8 (1) Confused flour beetle-The insecticidal activity Tnbu y 2g 3g 22 was determined on the confused flour beetle (Tribolium 5,000 82 46 50 confusum) by placing the beetles in 9.6 cm. Petri dishes TnphenyltmNhexylmaleamat"' 28 53 to which had been added one milliliter of acetone con- Triethyltin 354' diohloro 5,000 100 0 taining 1000 p.p.m. of the test compound and the acetone maleamlate 28 gg allowed to evaporate. The percent mortality of the beetles Tributyltir13,4dichloro 5, 000 100 1% was determined on the first and the fifth day and the maleamlate 2% 3 55 results are summarized in Table IV. Triphenyltin 3,4 dichloro 5, 000 99 32 T ABLE IV maleanilate 500 44 76 50 2O 84 Percent mortality Triphenyltin 3,4' dichloro 5, 000 90 22 succinanilate figg 22 Compound 1 day 5 days 6,000 100 0 Triethyltln N hexylmaleamate 100 100 Panogen-15 (Standard) 500 0 30 'Iriphenyltin N hexylmaleamate 100 100 50 34 6 Triethyltin 3' 4 dichloromaleanilate 100 100 Check Tributyltin 3 ,4 dichlorornaleanilate..- 70 90 Triphenyltin 3,4 dichloromaleanilate 80 90 't=Slight toxicity to seeds. 'Iriphenyltin 3,4 dichlorosuccinanilate 80 100 Table II shows that the compounds of Formula I are superior to the commercial seed disinfectant, Panogen-lS which is methylmercuric dicyandiamide. In addition, the compounds of the invention stimulated seed germination at low dosages which can be seen by comparing the percent of germination with that of the check.

Since both phenylmercuric N-hexylmaleamate and Panogen-IS are organomercurials, they were compared in the same test at lower dosages. The results are shown in Table III.

Table IV sohws that the tin compounds of the invention are extremely elfective against the confused flour beetle particularly since Chlordane, a commercial insecticide, at 5000 p.p.m. show only 35% and mortality after 2 and 6 days, respectively.

(2) Drosophilia melanogaster.-The test compounds were applied as thin film of acetone containing 1000 p.p.m. and 500 p.p.m. of the compounds to the walls of a test tube (25 mm. X 200 mm.) and 10 flies (Drosophilz'a melanogaster) were released into the test tube which was then stoppered with absorbent cotton. The flies had sufli- 7 cient food for three days. The percent mortality was determined after 24 and 48 hours and in some instances the knock-down time was determined. The results are summarized in Table V.

activity of the compounds of Formula I by measuring the compounds into 10 ml. test tubes containing suificient nutrient broth to give final concentrations of 5000, 500 and 50 p.p.m. of the compounds. 1 ml. of a stock prepa- TABLE V Percent Mortality Knock- Dosage, down Compound p.p.m. 24 hrs. 48 hrs. time Triethyltin N-hexylmaleamateggg {g8 mo 10 mm Tributyltin N-hexylmaleamate 28g: fig j Triethyltin 3,4-dichloromaleanilate m min Tributyltin 3',4-dichloromaleanilate 19% a 3;; S Phenylmercuric N hexylmaleamate l, 000 88 100 Tributyltin 3,4'-dichlorosuccinanilate 100 90 100 Tributyltin 3-chlorosuccinanilate 100 75 100 Tributyltin 3-C F -suocinanilate 100 83 100 Tributyltin 4-chloro-3-C Frsuccinanila 100 71 100 Tributylttn N ,N-diethylsuccinamate. 100 76 100 Tributyltin N,N dipropylsuccinamate 100 82 100 Tables IV and V show that the compounds of Formula I are extremely effective insecticides.

(3) Mexican bean beetle.The insecticidal activity was determined on the Mexican bean beetle by the leaf dip method at doses of 1,000, 500 and 250 p.p.m. of the test compounds, and the percent mortality of the beetles was determined on the fifth day. The results are summarized in Table V(A) and they show the extreme effectiveness of these compounds.

D. Acaricidal activity Leaves infested with two-spotted spider mites, Tetranychus bimaculatus, were dipped momentarily into distilled water solutions or suspensions containing 1000 p.p.m. of the test compound and then placed into a rack to drip dry. The test racks were held at a temperature of 78 to 80 F. and percent mortality was determined after 24 and 48 hours.

The results are summarized in Table VI.

TABLE VI Percent mortality Compound 24 hrs. 48 hrs.

Phenylmercuric N-hexylmaleamate 43 72 Triethyltin N-hexylmaleamate- 92 99 Tributyltin N-hexylmaleamate- 50 100 Trlphenyltin N-hexylmaleamate. 35 24 Triethyltin 3 4-dichloromaleam1ate- 90 100 Tributyltin 3 ,4-dichloromaleanilate 100 100 Triphenyltin 3',4-diohloromaleamlate 87 19 Triphenyltin 3,4-dichlorosuecinan1late 14 11 Tributyltin 3 ,e-dichlorosuccinanilate- 100 100 Tributyl'tin 3-chlorosuccinanilate 100 100 'Iributyltin 3-C F -succinanilatm 100 100 Tributyltin 4 ohloro-3-CzF-succm late 100 100 Tributyltin N,N-diethylsuecinamate 100 100 Tributyltin N,N-dipropylsuccinamat 100 100 Kelthane 100 100 Table VI shows that the compounds of Formula I possess acaricidal activity, particularly the compounds where R is alkyl.

E. Soil-inoculum broth culture This test determines the fungicidal and bactericidal ration of soil providing an inoculum source for a mixture of organisms, was added to each tube and the test tubes were allowed to stand for several days. The extent of growth of fungi and bacteria which is evidenced by turbidity in the test tubes was determined periodically. The ratings were based on a scale of 0 (complete control), to 5 (no control). The results are summarized in Table VII.

TABLE VII Turbidity index at- 5,000 500 ppm. p.p.rn.

Compound p.p.n1.

Phenylmercuric N-hexylmaleamate Triethyltln N-hexylmaleamete. Trlbutyltin N-hexylmaleamate Triphenyltin N-hexylmaleama Triethyltin 3' .4'-dichloromaleanil Tributyltin 3 ,4-dicl1loromaleanilate 'lriphenyltin 3',4-dichloromaleanllat Triphenyltin 3,4-diehlorosuccinanilate Trlbutyltin 3,4-diohlorosuccinanllate Trlbutyltln 3-chlorosuccinanilate Trlbutyltiu 3-CFa-succinanilate Tributyltin 4-chloro-3'-C F -succ Tributyltin N N-dlpropyl succlnamate- Tetrachloro-p-benzoquinone (Sperg0n) Table VII shows that the compounds of Formula I are effective in this test, particularly those wherein R is alkyl.

F. Bactericidal activity TABLE VIII Dosage, Inhibition Zone in mm.

ppm.

Compound S. au-reus S. typhosa Triethyltin N-hexylmaleamate. 2, 000 8. 5 9. 5 Triphenyltln N-hexylmalcamate..-. 2, 000 8. 0 0 Triethyltiu 3 ,4-dichloromaleanilate 2, 000 8. 0 10. 5 Tributyltin 3' maleanilate. 2, 000 8. 0 0 Tnphenyltm 3 maleanilate. 2, 000 8. 5 0 Trlphenyltlu 3' succinanilate. 2, 000 8. 5 0 Tributyltin 3',4

sucoinanilate 1, 000 0 0 Trlbutyltin 3-ehlorosuoclnanllate 1, 000 4. 5 0 Tributyltin 3-CF -succ1nanllat 1,000 5 0 Tributyltin 4'-chloro-3'-CF succlnanilate 1, 000 3 0 Tributyltin N,N-diethyl succtnamate 1, 000 5 Tributyltln N,N-dlpropy1 succiuamate l, 000 4 0 9 Table VIII shows that the compounds are eifective against gram positive bacteria and that the triethyltin compounds are also eflective against gram negative bacteria, which are diflicult to control.

toxicity rating based on the scale of (no injury), to 10 (plants killed), was made and the actual number of seeds germinating was determined. The results are summarized in Table 1X.

TABLE IX Johnson Compound Beet Tomato Radish Grass Oats Wheat Cotton Phenylmercuric N -hexylmaleamate:

Germ 9 21 11 9 13 PR" 101: 8t 7t 7!; 5s 2 1 Triethyltm 3,4 dichloromaleanllate:

St a 13 1 18 1g 3 u 2 1 Tributyltin 3,4 dichloromaleanilate:

Germ 23 2(7) 1% 2g 22 13 5 0 0 Tripheuyltin 3,4 dichloromaleanilate (rgrgrm 13 13 23 1(5) 18 13 12 0 0 Tributyltin N-hexylmaleamate:

1 a 15 it t t 3 5 S 1 Tributyltin 3,4-diohlorosuccinanilate:

2 Tributyltin 8-ch1orosuccinanilate:

1 Tributyltin 3-CFa-succinanilate:

gi i 18 1 93 94 g g 45 5 Tributyltin 4-C1-3-C Fa-succinanilate:

1 18 it 8 t t 8 Tributyiiifiiiiikiiiriyifibifiaial""- %E 0 0 8 0 80 72 65 PR 10 10 10 10 5 2 0 Tributyltin N ,N-dlpropyl succmamate:

t; toxicity; s stunting; %E percent of seeds germination compared to control; Germ N o. oi seeds germmating.

F. Pre-emergence herbicidal activity Soil flats were carefully filled with soil and were planted with seeds of beets, tomato, radish, oats and wheat, seeds of Johnson grass and 20 seeds of cotton which were then covered with a uniform amount of soil. The test compounds were prepared as 25% wettable powders using a premix consisting of 92% Hi-Sil 233 (fine hydrated silica pigment), 4% of Monasperse N (lignosulfonates), and 4% of Pluronic L-61 (polypropylene glycol-polyethylene glycol). The desired amount of the said powder was diluted with 200 ml. of water for a dosage of 10 pounds of compound per acre and the flats were uniformly drenched therewith. The flats were covered with newspaper for four days and the flats were watered for the 3 days after first emergence. After two weeks, a phyto- As can be seen from Table 1X, the organomercuric and trialkyltin compounds have good pre-emergence herbicidal activity and are useful in cotton and wheat crops which are resistant thereto.

G. Post-emergence herbicidal activity TAB LE X Pots Phytotoxicity rating-Flats Dosage, Compound p.p.m Cotton Crabgrass Beans Beets Tomato Radish Flax Rye Oats Wheat Triethyltin N-hexylmaleamate g l 3 g 2 4 1 10 10 10 10 4 9 2 Tnphenyltm N-hexylmaieamate. f i 5 m 10 10 3 6 1 Trlethyltln 3',4-dichloromaleanilate g 3 g g g Tributyltiu 3,4-dichloromaleanjlate g 3: i g g g 2 i Triphenyltin 3,4-dichloromaleanilate i g V i 2 3 f g i Tripheuyltin 3,4-dichlorosuccinanilate g i g 2 g g Phenylmercuric N-hexylmaleamate "6 "6 2 "a "i6 "i Solvent check 0 0 0 0 0 0 8 1 0 0 TABLE XI Phytotoxicity Rating Dosage, LbJAcre Beets Tomato Radish Oats Wheat Cukes Pigweed Tributyltin 3,4-dichlorosuceinanilate 1. 9 10 10 10 2 2 10 10 Trlbutyltin 3'chlorosuceinanilate.- 1. 9 10 1O 10 2 2 10 10 Tributyltin 3'-O F -succinanilate 1. 9 9+ 10 10 2 1 10 10 Tributyltin 4-ohlor0-3-GFa-succinanilate 1. 9 9 10 10 1 1 10 10 Tributyltin N,Ndiethyl succinamate- 1. 9 10 10 10 4 2 10 10 Tributyltin N,N-dipropyl sucoinamate 1.9 9+ 10 10 2 1 10 10 Phytotoxlcity Rating Johnson Grass Dosage, Red Soy Lb./Acre Sotarla Rice Small Med. Lge. Kidney Bean Cotton Tributyltin 3,4-dlchlorosucclnanllate 1. 9 10 1 10 10 10 10 5 4 Tributyltin 3-chlorosuccinanilate 1. 9 1 10 9 10 8 9 7 Tributyltin 3-CF suceinanilate 1. 9 10 1 9 9 10 9 7 4 Tributyltin 4-chloro-3-CFa-succinanilat 1. 9 10 1 10 9+ 10 10 7 4 Tributyltin N,N-diethyl succinamate.. 1. 9 8 2 8 7 9 9 7 5 Tributyltln N,N-dipropy1 succinamate. 1 9 8 2 8 9+ 10 7 E10 0 As can be seen from Tables X and XI, the organornetal- 8. A compound of claim 1 wherein R is -CH CH lic compounds of the invention possess excellent postemergence herbicidal activity.

Various modifications of the products and compositions of the invention may be made without departing from the spirit or scope thereof, and it is to be understood that the invention is to be limited only as defined in the appended claims. 1

We claim:

1. An organometallic compound of the formula wherein R is selected from the group consisting of the cisand transform of CH=OH- and CH -OH and R are selected from the group consisting of alkyl of 1 to 10 carbon atoms, halogenated alkyl of 1 to 10 carbon atoms, alkenyl and alkyn'yl of 2 to 10 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, naphthyl, phenyl and phenyl substituted w selected from the group consisting of halogen, lower alkyl and halogenated lower alkyl of 1 to 7 carbon atoms, hydroxy, lower alkoxy of 1 to 7 carbon atoms and nitro and R' is selected from the group consisting of hydrogen, alkyl of 1 to 10 carbon atoms, halogenated alkyl of 1 bon atoms, cyclo-alkyl of 4 to 8 carbon atoms, naphthyl, phenyl and phenyl substituted with at least one substituent selected from the group consisting of halogen, lower alkyl and halogenated lower alkyl of 1 to 7 carbon atoms, hydroxy, lo nitro, M is selected and tin and n and m is not greater than 4.

2. A compound of claim 1 wherein R is the cis form of -CH=CH, R is is 1, R" is phenyl and R'" is hydrogen.

3. A compound of claim 1 wherein R is the cis form of -CH=CH--, R is ethyl, n is 3, M is tin,'m is 1, R"' is hexyl and R' is hydrogen.

4. A compound of claim 1 wherein R is the cis form of -CH=CH-, R

is hexyl and R' is hydrogen.

from the group consisting of mercury are integers from 1 to 3 and m-i-n ith at least one substituent.

wer alkoxy of 1 to 7 carbon atoms and phenyl, n is 1, M is mercury, m

R is phenyl, n is 3, M is tin, m is l, R" is 3,4-dichlorophenyl and R' is hydrogen.

9. A compound of claim 1 wherein R is the cis form of CH:CH, R is butyl, n is 3, M is tin, m is 1, R" is hexyl and R is hydrogen.

10. A compound of claim 1 wherein R is -CH CH R is butyl, n is 3, M is tin, m is 1, R' is hydrogen and R" is 3,4-dichl0ropheny1.

11. A compound of claim 1 wherein R is -CH --CH R is butyl, n is 3, M is tin, m is l, R is hydrogen and .R" is 3-ch1orophenyl.

12. A compound of claim 1 wherein R is R is butyl, n is 3, M is tin, m is 1, R' is hydrogen and to 10 carbon atoms, alkenyl and alkynyl of 2 to 10 caris phenyl, n is 3., M is tin, m is 1,

5. A compound of claim 1 wherein R is the cis form of CH=CH-, R is ethyl, n is 3, M is tin, m is 1,

R" is 3-trifluoromethylphenyl.

13. A compound of claim 1, wherein R is -CH -OH R is butyl, n is 3, Mis tin, m is 1, R' is hydrogen and R" is 4-chloro-3-trifluoromethylphenyl.

14. A compound of claim l'wherein R is -CH QH R is butyl, n is 3, M is tin, m is 1 and R and R are ethyl.

15. A compound of claim 1 wherein R is n-propyl.

References Cited UNITED STATES PATENTS 2,672,472 3/1954 Yale 260-434 2,977,379 3/ 1961 Dorfeltet a1. 260-4297 3,067,167 12/ 1962 Lynn et a1 260429.7 X 3,355,469 11/ 1967 Herbstman 260-429.7

OTHER REFERENCES Kosolapotf, Chemical Abstracts (1962), vol. 58, p. 7962(f).

U.S. C1.X.R. 

